A theory for predicting the maximum spoutable height in a spouted bed

A theory is presented for predicting the maximum spoutable height, in a spouted bed where fluidization of the annular solids limits the penetration of the fluid jet entering the bed. The quantity (H_md_s/(D – d) is found to be a function of d_s/D_c only for spherical particles and \[ \frac{{H_m d_S }} {{(D_c^2 - d_S^2 )}} = 0.345\left( {\frac{{d_S }} {{D_c }}} \right)^{ - 0.384} \] where the spout diameter is calculated using McNab's correlation⁽⁷⁾. Insertion of McNab's correlation into Equation (1) shows that H_m is proportional to D and the effect of d_p on H_m varies from d to d as the particle Reynolds number increases assuming 1 ≥ (d_s/D). Using experimental value of d_s, the calculated values of H_m differ from the experimental ones by 8.5% on average. When small particles are spouted with air, the penetration of the jet is limited by the formation of a slug in he spout and the theoretical value provides an upper limit for H_m.     

Oxidative coupling of methane over a La2O3/CaO catalyst. Optimization of reaction conditions in a bubbling fluidized-bed reactor

Oxidative coupling of methane over a La₂O₃/CaO catalyst was investigated in laboratory-scale fluidized-bed reactors (ID = 5 and 7 cm) in the following range of reaction conditions: T = 700 – 880°C, P = 41 – 72 kPa and P = 6 – 29 kPa. The maximum C₂₊ selectivity and yield amounted to 73.8% (T = 800°C, X = 13.1%, Y = 9.7%) and 16.0% (T = 840°C, X = 34.0%, S = 47.2%), respectively. Axial gas concentration profiles revealed that C₂₊ selectivity was not only influenced by oxidative consecutive reactions, but also by steam reforming of ethylene. When diluting the catalytic bed (m_cat = 145 g) with quartz (m = 200 and 400 g), a slight decrease of the selectivity (1–2%) was observed. The dilution of the feed gas with nitrogen only led to only a small increase (< 2%) of the C₂₊ selectivity.     

The higher alcohol synthesis over promoted Cu/ZnO catalysts

Alkali oxides added to methanol catalysts increase the formation of ethanol, n-propanol and isobutyl alcohol. This result has been known for many years, yet few quantitative studies have been reported in the literature. Data obtained on a commercial copper-zinc oxide catalyst promoted with K₂ CO₃ are presented and compared with published work. The optimum promoter concentration was about 0.5% by weight. The H₂ to CO feed ratio was important in determining the higher alcohol selectivity. The rate of production of isobutyl alcohol varied as p p while for methanol, ethanol and n-propanol both exponents were positive and less than 1.6. Decreasing the hydrogen to carbon monoxide ratio from 2 to 0.5 more than doubled the isobutyl alcohol selectivity. Chain growth schemes predicting the higher alcohol selectivity are presented and estimates of the parameters are given.     

Tearing mode interlaminar fracture toughness of composite materials

The Simplified Split Cantilever Beam (SSCB) is proposed in this work and compared with the Split Cantilever Beam (SCB) to obtain the tearing mode interlaminar fracture toughness. The materials considered are single‐fiber system composites and interply hybrid composites. For interply hybrid composites, three different types of stacking sequence for SSCB specimens, which are [0/0//0],[0/0//0]. and [0/0//0], are tested to compare their suitability. Finite element analysis combined with a modified crack closure integral has been applied to separate the different components of the strain‐energy release rate. In addition, the method of compliance calibration was used to calculate Gc values. The effects of crack growth, initial crack length, specimen width, and number of glass fiber plies were also studied. The results show that SSCB testing has a more dominant Mode III component and more stable Gc values than SCB testing. For SSCB testing, the crack growth and the specimen width for the range considered have no clear effects on the interlaminar fracture toughness, but the initial crack length should be carefully selected to obtain corrected values. The tearing mode interlaminar fracture toughness of interply hybrid composites is higher than that of carbon/epoxy composites, and the three different types of stacking sequence considered are all suitable to approximate the Mode III interlaminar fracture toughness for interply hybrid composites.     

Nonlinear programming methods to determine surface free energy components of polymers using harmonic mean approximation

The dispersion and polar surface free energy components, γ and γ, and the critical surface free energy, γ_c, of polymers were determined from contact angle data by the application of a nonlinear programming method using harmonic mean approximation. The surface free energy components of the probe liquids, γ and γ, which reflect the conditions of the maximized interaction parameter, Φ, were also simultaneously determined by this method.     

Forced oscillations in continuous flow stirred tank reactors with nonlinear step growth polymerization

The self-step growth polymerization of RA_f monomers in homogeneous, continuous flow stirred tank reactors (HCSTRs) is simulated under conditions of periodic feed concentration (with frequency ω and amplitude α). By having periodic operation, the polydispersity index of the polymer is found to increase by about 35% over the values at steady state. Periodic operation of HCSTRs is found to lead to gelation only for certain values of the frequency and the dimensionless residence time τ^*. Gelling envelopes have been obtained to give conditions under which HCSTRs should be operated. These envelopes can be described in terms of two critical dimensionless residence times, τ and τ such that nongelling operation is always ensured when τ^* < τ. For τ^* > τ, periodic operation always leads to gelation, and HCSTRs cannot be used. For τ < τ^* < τ, the gelling behavior is found to depend on the functionality f, amplitude α, and the dimensionless residence time τ^*.     

Elastic characteristics of branched-network polymers

The computed dependencies of elastic characteristics of branched-network polymers were obtained on the basis of the Takayanagi series model. The moduli ratio (λ) for branched-network and branched polymers increases as a result of an increase of the moduli ratio of network and branched phases (E/E) and the network phase fraction (V_net). The λ-increase as a function of V_net is larger than in the case of the E/E dependence. On the basis of computed dependencies, the experimental results for the radiation crosslinked SBS block copolymer were considered. The experimental results agree with the computed de-pendencies for the hetergeneous branched-network polymers with E/E ≈︁ 20. The influence of entanglements on the elastic characteristics of branched-network polymers is discussed. © 1996 John Wiley & Sons, Inc.     

Homogeneous and heterogeneous catalytic reactions in a cobalt oxide/graphite air electrode. Part IV. Mechanistic studies on a ring-disk carbon electrode in alkaline solution

The redox properties of HCoO on a glassy carbon electrode in the absence and presence of hydrogen peroxide have been investigated by using cyclic voltammetry and UV-Vis spectroscopy in alkaline solution. Corresponding rotating ring-disk experiments showed that the disk current increased by about 60% in the presence of HCoO, confirming the important role played by HCoO in the homogeneous decomposition of hydrogen peroxide.     

Über die Katalyse der Cooxidation von cis-Oct-4-en und n-Butyraldehyd

The Catalysis of the Co-Oxidation of cis-Oct-4-ene and n-Butyric Aldehyde The co-oxidation of cis-oct-4-ene and n-butyric aldehyde in the absence of catalysts, or in the presence of molybdenum and Co(acac)₃, resp., was studied in dependence on the aldehyde/olefin ratio, on the temperature and other reaction conditions. Under the same conditions, the noncatalyzed co-oxidation converted 50%, the MoO₂(acac)₂-catalyzed one 68%, and the Co(acac)₃-catalyzed one 40% of the reacted olefin into the epoxide. The cis/trans-epoxide ratio in the molybdenum-catalyzed co-oxidation was nearly 2 independent of the aldehyde/olefin ratio. In the non-catalyzed co-oxidation the cis/trans-epoxide ratio depends linearly on the aldehyde/olefin ratio (cis/trans E. = 0,58 + 0,90 n/n). From these dependences we can conclude that the homolytic mechanism of epoxide formation decreases and the polar mechanism (Priležaev-reaction) increases with increasing aldehyde/olefin ratio. Optimization of the epoxide yields according to a Box-Hunter experimental plan gave the following reaction conditions to yield 95% epoxide based on reacted olefin: 70°C, Δn_S/n = 0,49, n/n = 3,5 · 10⁻³, n/n = 0,53. The co-oxidation in the presence of other molybdenum catalysts of the chloro-nitrosyl-complex type and of the carbonyl-complex type as well as the co-oxidation with other aldehydes were studied, too.     

The Electrolytic “Sintering” of Nickel Powder

Adherent and coherent deposits of nickel sponge similar to sintered nickel may be made from sulphate, chloride, fluoborate or sulphamate nickel plating solutions containing nickel powder in suspension, providing the concentration of free acid is maintained sufficiently high to inhibit co-depesition of Ni(OH) In nitrate solution, cathodic reduction of nitrate and deposition of Ni(OH)₂ predominates.     

Intrinsic birefringence of nylon 6

Different values are reported in the literature for the intrinsic birefringence of the crystalline (Δn) and the amorphous (Δn) phases in nylon 6. Mostly, these values have either been determined by extrapolation (and then it is assumed that Δn = Δn) or calculated theoretically. In this study, intrinsic birefringence values Δn and Δn for nylon 6 were determined using the Samuels two-phase model which correlates sonic modulus with structural parameters. Three series of fiber samples were used: (1) isotropic samples of different degrees of crystallinity for estimation of E and E moduli at two temperatures. The following modulus values were obtained: 1.62 × 10⁹ and 6.66 × 10⁹ N/m² for 28.5°C, and 1.81 × 10⁹ and 6.71 × 10⁹ N/m² for ?20°C; (2) anisotropic, amorphous fiber samples for estimation of Δn = 0.076 and E = 1.63 × 10⁹ N/m² at 28.5°C; (3) semicrystalline samples of various draw ratios for estimations of Δn = 0.089 and Δn = 0.078. All measurements were carried out with carefully dried samples to avoid erroneous results caused by moisture.     

Regression‐based model for elastic constants of 2D braided/woven open mesh angle‐ply composites

The elastic constants of closed mesh braided/woven fabrics are generally obtained from finite element analysis, fabric geometry model, and modified classical laminate plate theory. These models are complex and often impractical for industrial design purposes and do not address the cases of open mesh braided/woven fabrics. This paper proposes an alternative to existing models and software packages. Simple regression‐based empirical equations were developed to obtain E_x, E_y, G_xy, and ν_xy of braided/woven fabrics at any angle‐ply angle using the braid/weave unit cell volume fraction (V_f0), the fiber volume fraction (V_f), and the elastic constants of an equivalent angle‐ply laminate (E, E, G, ν). Design equation predictions were verified by comparing them to a previously validated modified classical laminate plate theory (CLPT) model using various fiber/resin combinations. Excellent agreement was found for each set of results. POLYM. COMPOS., 26:152–164, 2005. © 2005 Society of Plastics Engineers     

Mass transport process for the adsorption of Cr(VI) onto water‐insoluble cationic starch synthetic polymers in aqueous systems

Dynamic adsorption behaviors between Cr(VI) ion and water‐insoluble amphoteric starches was investigated. It was found that the HCrO ion predominates over the initial pH ∼ 2–4, the CrO ion predominates over the initial pH ∼ 10–12, and both ions coexist over the initial pH ∼ 6–8. The sorption process occurs in two stages: the external mass transport process occurs in the early stage and the intraparticle diffusion process occurs in the long‐term stage. The diffusion coefficient of the early stage (D₁) is larger than that of the long‐term stage (D₂) for the initial pH 4 and pH 10. The diffusion rate of HCrO ion is faster than that of CrO ion for both processes. The D₁ and D₂ values are ∼ 1.38 × 10⁻⁷–10.1 × 10⁻⁷ and ∼ 0.41 × 10⁻⁷–1.60 × 10⁻⁷ cm² s⁻¹, respectively. The ion diffusion rate in both processes is concentration dependent and decreases with increasing initial concentration. The diffusion rate of HCrO ion is more concentration dependent than that of CrO ion for the external mass transport process. In the intraparticle diffusion process, the concentration dependence of the diffusion rate of HCrO and CrO ions is about the same. The external mass transport and intraparticle diffusion processes are endothermic and exothermic, respectively, for the initial pH 4 and pH 10. The k_d values of the external mass transport and intraparticle diffusion processes are ∼ 15.20–30.45 and ∼ −3.53 to −12.67 kJ mol⁻¹, respectively. The diffusion rate of HCrO ion is more temperature dependent than that of CrO ion for both processes. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2409–2418, 1999     

Influence of anionic form on thermal degradation of TMAHP–cellulose

Trimethylammoniumhydroxypropyl (TMAHP)–cellulose in 10 anionic forms (F^?, Cl^?, Br^?, I^?, HSO, NO, OH^?, HCO, H₂PO, CH₃COO^?) was prepared, and the influence of each anion on thermal degradation in inert atmosphere was studied. With the help of dynamic and isothermal thermogravimetry (TG) it was found that H₂PO ions had the greatest retarding effect on TMAHP–cellulose degradation. From the values of rate constants it can be seen that all ionic forms of TMAHP–cellulose have the starting rate of thermal degradation greater than unmodified cellulose. The calculated values of activation energy of thermal degradation for different ionic forms are decreasing in following sequence: H₂PO > F^? > NO > I^? > Br^? > HCO > Cl^? > HSO > OH^? > unmodified cellulose > CH₃COO^?. From the results of pyrolyse measurements in combination with gas chromatography and mass spectrometry (Py–GC–MS) it follows that the products of the elimination of quarternary ammonium salts are trimethylamine, 3-hydroxy-2-propanone, and, in the case of OH^? form, water. In all other ionic forms the third product is the corresponding acid.     

Measuring the amount of crystallinity in solutions using DSC

The amount of solid that forms in a solution at temperatures below the cloud point, is an important quantity in the design of crystallisation processes. A new method using differential scanning calorimetry (DSC) to measure the fraction of crystallised solution, α ' is proposed. A very good agreement is obtained between the data measured by the new calorimetric method and using alternative techniques. A simple graphic version of the calculation procedure is also presented. It is shown to produce quick and fair estimates for the solid fraction by a simple analysis of a plot of enthalpy variation with temperature.     

Mechanical properties of polyethylene/ethylene vinyl acetate filled with calcium carbonate

The tensile behavior of polyethylene/ethylene vinyl acetate (PE/EVA) polymer blends filled with calcium carbonate (CaCO₃) was studied using tensile and viscoelastic tests. The relations between tensile properties (modulus, strength, etc) of oriented and unoriented PE/EVA-CaCO₃, and void volume of polymer/CaCO₃ interface, PE/EVA blend ratio, and CaCO₃ content were investigated. The results indicated that the tensile strength and elongation of PE/EVA-CaCO₃ decreased with CaCO₃ content and PE blend ratio for unoriented PE/EVA-CaCO₃ systems. In the case of oriented samples, the relative modulus (E/E, where E and E are the modulus of oriented composites and the modulus of oriented matrix, respectively) of PE/EVA-CaCO₃ is larger than that of PE/CaCO₃ by increasing the EVA content relative to PE and CaCO₃. The value of E/E can be simply expressed as the function of void volume and CaCO₃ modulus to polymer matrix modulus.     

Modeling the influence of mineral rocks,active in different hot gas conditioning systems and technologies,on the production of light α-olefins

A mechanistic reaction model of the pyrolysis of vaporized n-heptane in the presence of steam (P ≈? 18&–32 kPa) is developed based on overall first-order decomposition kinetics, which satisfactorily describes the experimental data. The mechanistic model predicted that calcined, naturally occurring and readily available mineral rocks, Swedish quarried calcium oxide (quicklime) and Norwegian (Norsk Hydro) magnesium oxide (dolomitic magnesium oxide) applied as the catalytic materials increase the conversion of the vaporized feedstock (P = 2.9–4.7 kPa) without changing the distribution of light α-olefins (i.e., C₂H₄, C₃₊, C₄H₈), compared to pyrolysis in an empty reactor viz. thermal steam-cracking. The simulation calls attention to the fact that the endothermic pyrolysis reaction of the alkane n-heptane is proceeding not only in the homogeneous gas-phase but also on the mineral particles (catalytic cracking) with the same mechanism.     

Modellrechnungen zum Gegenioneneinfluß auf die kationische Polymerisation; Geometrieoptimierung und Verhalten gemischter Halogenoantimonate SbClnBr

Model Calculations on the Counterion Effect in the Cationic Polymerization; Geometry Optimization and Behaviour of the Mixed Halogenoantimonates SbCl_nBr . The CNDO/2 method including geometry optimization with respect to the energy has been applied to calculate the structure and the electronic properties of the complex anions SbCl_nBr. Independently on the composition of the anions the bond lengths Sb-X (X = Cl, Br) remain those of the pure antimonates. The HOMOs are delocalized over the ligand sphere. They mainly contain components of Br and are lifted by increasing Br amount. The LUMOs have central atom character and are lowered by Br. Charge distribution and Wiberg bond indices indicate extra easy cleavage of the Sb-Br bond if Cl holds a trans position to Br. The computed data agree with spectral properties, the acceptor behaviour and the decay trend of the antimonates SbCl_nBr.     

Electrochemical synthesis and properties of poly(3‐methylthiophene): Novel synthesis of poly(3‐methylthiophene) with pentachlorostannate and hexachloroantimonate

Poly(3‐methylthiophene) (P3‐MeT) doped with different anions were prepared electrochemically in the presence of tetraalkylammonium salts. The new poly(3‐methylthiophene) SnCl and SbCl (P3‐MeT SnCl₅ and P3‐MeT SbCl₆) were prepared electrochemically using tetra‐n‐butylammonium pentachlorostannate and tetra‐n‐butylammonium hexachloroantimonate as the supporting electrolytes. The effect of current density, salt concentration, reaction temperature, and the nature of solvents on the polymer yield and polymer conductivities have been investigated. Cyclic voltammetry of poly(3‐methylthiophene) has been examined at platinum electrode in 1,2‐dichloroethane medium containing n‐Bu₄NSnCl₅, Bu₄NSbCl₆, and Bu₄NClO₄ as the supporting electrolytes in the range of −1.0 to 1.7 V versus SCE in the presence and absence of 3‐methylthiophene. Electrical conductivity, magnetic susceptibility measurements, and structural determination by elemental analysis and infrared studies were also made. Scanning electron microscopy revealed a globular, branched, fibrous and a spongy, fibrous morphology of poly(3‐methylthiophene) SnCl, ClO, and SbCl, respectively. The thermal analysis of the polymers was also investigated. Possible causes for the observed lower conductivity of these polymers have also been discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 91–102, 1999     

Several features of vinyl chloride–diallyl phthalate suspension copolymerization

Vinyl chloride–diallyl phthalate (VC–DAP) suspension copolymerization was carried out in a 5‐L autoclave and 200‐mL stainless steel vessel at 45°C. The apparent reactivity ratios of VC–DAP suspension copolymerization system were calculated as r_VC = 0.77 and r_DAP = 0.37. It shows that VC–DAP copolymer contains no gel when the feed concentration of DAP (f) is lower than a critical concentration (f_cr, inside the range of 0.466–0.493 mmol/mol VC at 80–85% conversion), the polymerization degree (DP) of copolymer increases with the increase of f and conversion. VC–DAP copolymer is composed of gel and sol fractions when f is larger than f_cr. The DP of sol fraction decreases as f increases, but the gel content and the crosslinking density of gel increase. The gel content also increases as conversion increases. The results also show that the index of polydispersity of molecular weight of sol changes with f, a maximum value appears when f is close to f_cr. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 156–162, 2000